The effect of the electrospinning process parameters on the morphology, alignment, and self-organization of the fibers into bundles and/or yarns are outlined. The fabrication of polylactide materials containing ionic drugs by electrospinning is emphasized. The main approaches used for the preparation of electrospun drug-loaded materials: electrospinning of a mixed solution containing the polymer(s) and the drug(s) or dual spinneret electrospinning of separate drug-containing solutions are compared. The latter approach allows the obtaining of drug-loaded fibrous materials while avoiding the drug interaction. The potential application of the obtained materials containing ionic drugs as wound dressings is outlined.